Certain polyepoxide treated derivatives of monoepoxide-amine modified-resins, and method of making same



United States Patent 1 2,864,792 CERTAIN POLYEPOXIDE TREATED DERIVATIVES 0F MONOEPOXIDE-AMINE MODIFIED-RESINS, AND METHOD OF MAKING-SAME Melvin De Groote, St. Louis, and Kwan-Ting Shen, Brentwood, Mm, assignors to Petrolite Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Original application June 10, 1953, Serial No. 360,841. Divided and this application September 11, 1956, Serial No. 609,091

12 Claims. (Cl. 260-45) The present invention is a continuation-in-part of our copending application, Serial No. 350,531, filed April 22, 1953, now U. S. Patent 2,771,430, and a division of our copending application Serial No. 360,841, filed June 10, 1953, now U. S. Patent 2,792,360.

Our invention is concerned with new chemical products or compounds useful as demulsifying agents in processes or procedures particularly adapted for preventing, breaking or resolving emulsions of the water-in-oil type and particularly petroleum emulsions. Our invention is also concerned with the application of such chemical products or compounds in various other arts and industries as well as with methods of manufacturing the new chemical products or compounds which are of outstanding value in demulsification.

The present invention is concerned with a 3-step manufacturing process involving (1) condensing certain phenol aldehyde resins, hereinafter described in detail, with certain basic non-hydroxylated secondary monoamines, hereinafter described in detail, and formaldehyde; (2) oxyalkylation of the condensation product with certain monoepoxides, hereinafter described in detail; and (3) oxyalkylation of the previously oxyalkylated resin condensate with certain nonaryl polyepoxides, also hereinafter described in detail.

The present invention is characterized by the use of compounds derived from diglycidyl ethers which do not introduce any hydrophobe properties in its usual meaning but in fact are more apt to introduce hydrophile properties. Thus, the diepoxides employed in the present invention are characterized by the fact that the divalent radical connecting the terminal epoxide radicals con- 1 tains less than 5 carbon atoms in an uninterrupted chain.

The diepoxides employed in the present process are obtained from glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, glycerol, diglycerol, triglycerol, and similar compounds. Such products are Well known and are characterized by the fact that there are not more than 4 uninterrupted carbon atoms in any group which is part of the radical joining the epoxide groups. Of necessity such diepoxides must be nonaryl or aliphatic in character. The diglycidyl ethers of co-pending application, Serial No. 350,531, are invariably and inevitably aryl in character.

The diepoxides employed in the present process are usually obtained by reacting a glycol or equivalent compound, such as glycerol or diglycerol, with epichlorohydrin and subsequently with an alkali. Such diepoxides have been described in the literature and particularly the patent literature.

Reference to being thermoplastic characterizes products as being liquids at ordinary temperature or readily convertible to liquids by merely heating below the point of pyrolysis and thus differentiates them from infusible resins. Reference to being soluble in an organic solvent means any of the usual organic solvents such as alcohols, ketones, esters, ethers, mixed solvents, etc. Reference to solubility is merely to differentiate from a reactant which is not soluble and might be not only insoluble but also infusible. Furthermore, solubility is a ICC factor insofar that it sometimes is desirable to dilute the compound containing the epoxy rings before reacting with an oxyalkylated amine condensate. In such instances, of course, the solvent selected would have to be one which is not susceptible to oxyalkylation, as, for example, kerosene, benzene, toluene, dioxane, possible various ketones, chlorinated solvents, 'dibutyl ether, dihexyl ether, ethyleneglycol diethylether, diethyleneglycol diethylether, and dimethoxytetraethyleneglycol.

The expression epoxy is not usually limited to the 1,2-epoxy ring. The 1,2-epoxy ring is sometimes referred to as the oxirane ring to distinguish it from other epoxy rings. Hereinafter the ford epoxy unless indicated otherwise, will be used to mean the oxirane ring, i. e., the 1,2-epoxy ring. Furthermore, where a compound has two or more oxirane rings they will be referred to as polyepoxides. They usually represent, of course, 1,2- epoxide rings or oxirane rings in the alpha-omega position. This is a departure from the standpoint of strictly formal nomenclature as in the example of the simplest diepoxide which contains at least 4 carbon atoms and is formally described as 1,2-epoxy-3,4-epoxybutane(1,2-3,4 diepoxybutane) It well may be that even though the previously suggested formula represents the principal component, or components, of the resultant or reaction product described in the previous text, it may be important to note that somewhat similar compounds, generally of much higher molecular weight, have been described as complex resinous epoxides which are polyether derivatives of polyhydric compounds containing an average of more than one epoxide group per molecule and free from functional groups other than epoxide and hydroxyl groups. The compounds here included are limited to the monomers or the low molal members of such series and generally contain two epoxide rings per molecule and may be entirely free from a hydroxyl group. This is important because the instant invention is directed towards products which are not insoluble resins and have certain solubility characteristics not inherent in the usual thermosetting resins. Simply for purpose of illustration to show a typi cal diglycidyl ether of the kind herein employed reference is made to the following formula:

or if derived from cyclic diglycerol the structure would be thus:

or the equivalent compound wherein the ring structure involves only 6 atoms, thus:

Commercially available compounds seem to be largely preceding, or low molal polymers thereof, it becomes ob-.

vious the reaction can take place with any oxyalkylated phenolaldehyde resin condensate by virtue of the fact' that there are always present either phenolic hydroxyl radicals or alkanol radicals resulting from the oxyalkylation of the phenolic hydroxyl radicals; there may be present reactive hydrogen atoms attached to a nitrogen atom or an oxygen atom, depending on whether initially there was present a hydroxylated group attached to an amino hydrogen group or a secondary amino group. In any event there is always a multiplicity of reactive hydrogen atoms present in the oxyalkylated amine-modified phenol-aldehyde resin.

To illustrate the products which represent the subject matter of the present invention reference will be made to a reaction involving a mole of the oxyalkylating agent, i. e., the compound having 2 oxirane rings and an oxyalkylated amine condensate. Proceeding with the example previously described it is obvious the reaction ratio of 2 moles of the oxyalkylated amine condensate to one mole of the oxyalkylating agent gives a product which may be indicated as follows:

(Oxyalkylated (Oxyalkylated condensate) condensate) in which n is a small whole number less than 10, and usually less than 4, and including 0, and R represents a divalent radical as previously described being free from any radical having more than 4 uninterrupted carbon atoms in a single chain, and the characterization oxyalkylated condensate is simply an abbreviation for the condensate which is described in greater detail subsequently.

Such final product in turn also must be soluble but solubility is not limited to an organic solvent but may include water, or for that matter, a solution of water containing an acid such as hydrochloric acid, acetic acid, hydroxyacetic acid, etc. In other words, the nitrogen groups present, whether two or more, may or may not be significantly basic and it is immaterial whether aqueous solubility represents an anhydro base or the free base (combination with water) or a salt form such as the acetate, chloride, etc. The purpose in this instance is to differentiate from insoluble resinous materials, particularly those resulting from gelation or cross-linking. Not only does this property serve to differentiate from instances where an insoluble material is desired, but also serves to emphasize the fact that in many instances the preferred compounds have distinct water-solubility or are distinctly dispersible in 5% gluconic acid. For instance, the products freed from any solvent can be shaken with 5 to 20 times their weight of 5% gluconic acid at ordinary temperature and show at least some tendency towards being self-dispersing. The solvent which is generally tried is xylene. If xylene alone does not serve then a mixture of xylene and methanol, for instance, 80 parts of xylene and 20 parts of methanol, or 70 parts of xylene and 30 parts of methanol, can be used. Sometimes it is desirable to add a small amount of acetone to the xylene-methanol mixture, for instance, 5% to of acetone. As oxyalkylation proceeds the significance of the basicity of any nitrogen group is obviously diminished.

The polyepoxide-treated condensates obtained in the manner described are, in turn, oxyalkylation-susceptible and valuable derivatives can be obtained by further re action with ethylene oxide, propylene oxide, ethylene imine, etc.

Similarly, the polyepoxide-derived compounds can be reacted with a product having both a nitrogen group and a 1,2-epoxy group, such as 3-dialkylaminoepoxypropane. See U. S. Patent No. 2,520,093, dated August 22, 1950, to Gross.

Although the herein described products have a number 4 of industrial applications, they are of particular value for resolving petroleum emulsions of the watcr-in-oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

The new products are useful as wetting, detergent and leveling agents in the laundry, textile and dyeing industries; as wetting agents and detergents in the acid washing of building stone and brick; as wetting agents and spreaders in the application of asphalt in road building and the like; as a flotation reagent in the flotation separation of various aqueous suspensions containing negatively I charged particles, such as sewage, coal washing waste water, and various trade wastes and the like; as germicides, insecticides, emulsifying agents, as, for example for cosmetics, spray oils, water-repellent textile finishes; as lubricants, etc;

As far as the use of the herein described products goes for purpose of resolution of petroleum emulsions of the water-in-oil type, we particularly prefer to use those which as such or in the form of the free base or hydrate, i. e., combination with water or particularly in the form of a low molal organic acid salt such as the gluconates or the acetate or hydroxy acetate, have sufiiciently hydrophile character to at least meet the test set forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

In the present instance the various condensation products as such or in the form of the free base or in the form of the acetate, may not necessarily be xylene-soluble although they are in many instances. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent preferably a watersoluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

For purpose of convenience, what is said hereinafter will be divided into eight parts:

Part 1 is concerned with the hydrophile nonaryl polyepoxides and particularly diepoxides employed as reactants;

Part 2 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation reaction to yield an amine-modified resin;

Part 3 is concerned with appropriate basic secondary monoamines free from a hydroxyl radical which may be employed in the preparation of the herein-described aminemodified resins;

Part 4 is concerned with reactions involving the resin, the amine, and formaldehyde to produce specific products or compounds which are then subjected to oxyalkylation with monoepoxides;

Part 5 is concerned with the oxyalkylation of the products described in Part 4, preceding;

Part 6 is concerned with reactions involving the two preceding types of materials and examples obtained by such reactions. Generally speaking, this involves nothing more than a reaction between two moles of a previously prepared oxyalkylated amine-modified phenolaldehyde resin condensate as described and one mole of a polyepoxide so as to yield a new and larger resin molecule or comparable product;

Part 7 is concerned with the resolution of petroleum emulsions of the Water-in-oil type by means of the pre viously described chemical compounds or reaction products; and

Part 8 is concerned with uses for the products herein described either as such or after modification, including any applications other than those involving resolution of petroleum emulsions of the water-in-oil type.

PART 1 Reference is made to various patents as illustrated in the manufacture of the nonaryl polyepoxides and particularly diepoxides employed as reactants in the instant invention. More specifically, such patents are the following: Italian Patent No. 400,973, dated August 8, 1941; British Patent No. 518,057, dated December 10, 1938; U. S. Patent No. 2,070,990, dated February 16, 1937, to Groll et al.; and U. S. Patent No. 2,581,464, dated January 8, 1952, to Zech. The simplest diepoxide is probably the one derived from 1,3-butadiene or isoprene. Such derivatives are obtained by the use of peroxides or by other suitable means and the diglycidyl ethers may be indicated thus:

In some instances the compounds are essentially derivatives of etherized epichlorohydrin or methyl epichlorohydrin. Needless to say, such compounds can be derived from glycerol monochlorohydrin by etherization prior to ring closure. An example is illustrated in the previously mentioned Italian Patent No. 400,973:

Another type of diepoxide is diisobutenyl dioxide as described in aforementioned U. S. Patent No. 2,070,990, dated February 16, 1937, to Groll, and is of the following formula HzC (|3CH2CH2C CH2 CH3 83H: The diepoxides previously described may be indicated by the following formula:

H R R H Hc0-[R]..'o-0H in which R represents a hydrogen atom or methyl radical and R" represents the divalent radical uniting the two terminal epoxide groups, and n is the numerical 0 or 1. As previously pointed out, in the case of the butadiene derivative, n is 0. In the case of diisobutenyl dioxide R is CH -CH and n is 1. In another example previously referred to R is CH OCH and n is 1.

However, for practical purposes the only diepoxide available in quantities other than laboratory quantities is a derivative of glycerol or epichlorohydrin. This particular diepoxide is obtained from diglycerol which is largely acyclic diglycerol, and epichlorohydrin or equivalent thereof in that the epichlorohydrin itself may supply the glycerol or diglycerol radical in addition to the epoxy rings. As has been suggested previously, instead of starting with glycerol or a glycerol derivative, one could start with any one of a number of glycols or polyglycols and it is more convenient to include as part of the terminal oxirane ring radical the oxygen atom that was derived from epichlorohydrin or, as might be the case, methyl epichlorohydrin. So presented the formula becomes:

In the above formula R is selected from groups such as the following:

It is to be noted that in the above epoxides there is a complete absence of (a) aryl radicals and '(b) radicals in which 5 ,or more carbon atoms are united in a single uninterrupted single group. R is inherently hydrophile in character as indicated by the fact that it is specified that the precursory diol or polyol HOROH must be water-soluble in substantially all proportions, i. e., water miscible.

Stated another way, what is said previously means that a polyepoxide such as is derived actually or theoretically, or at least derivable, from the diol HOROH, in which the oxygen-linked hy drogen atoms were replaced by H H H -OC-OH Thus, R(OH),,, where n represents a small whole number which is 2 or more, must be Water-soluble. Such limitation excludes polyepoxides if actually derived or theoretically derived at least, from water-insoluble diols or water-insoluble triols or higher polyols. Suitable polyols may contain as many as 12 to 20 carbon atoms or thereabouts.

Referring to a compound of the type above in the formula in which R is C H (OI-I) it is obvious that reaction with another mole of epichlorohydrin with appropriate ring closure would produce a triepoxide or, similarly, if R happens to be C H (OH) OC H (OH), one could obtain a tetraepoxide. Actually, such procedure generally yields triepoxides, or mixtures with higher epoxides and perhaps in other instances mixtures in which diepoxides are also present. Our preference is to use the diepoxides.

There is available commercially at least one diglycidyl ether free from aryl groups and also free from any radical having 5 or more carbon atoms in an uninterrupted chain. This particular diglycidyl ether is obtained by the use of epichlorohydrin in such a manner that approximately 4 moles of epichlorohydrin yield one mole of the diglycidyl ether, or, stated another way, it can be considered as being formed from one mole of di glycerol and 2 moles of epichlorohydrin so as to give the appropriate diepoxide. The molecular weight is approximately 370 and the number of epoxide groups per molecule are approximately 2. For this reason in the first of a series of subsequent examples this particularv Using laboratory procedure we have reacted diethylene The molecular weight of the product was assumed to be 230 and the product was available in laboratory quantities only. For this reason, the subsequent table referring to the use of this particular diepoxide, which will be referred to as diglycidyl ether B, is in grams instead of pounds.

Probably the simplest terminology for these polyepoxides, and particularly diepoxides, to differentiate from comparable aryl compounds is to use the terminology epoxyalkanes" and, more particularly, polyepoxyalkanes or diepoxyalkanes. The difficulty is that the majority of these compounds represent types in which a carbon atom chain is interrupted by an oxygen atom, and, thus, they are not strictly alkane derivatives. Furthermore, they may be hydroxylated or represent a heterocyclic ring. The principal class properly may be referred to as polyepoxypolyglycerols, or diepoxypolyglycerols.

Other examples of diepoxides involving a heterocyclic ring having, for example, 3 carbon atoms and 2 oxygen atoms, are obtainable by the conventional reaction of combining erythritol with a carbonyl compound, such as formaldehyde or acetone so as to form the S-membered ring, followed by conversion of the terminal hydroxyl groups into epoxy radicals.

PART 2 It is well known that one can readily purchase on the open market, or prepare, fusible, organic solvent-soluble, Water-insoluble resin polymers of a composition approximated in an idealized form by the formula H OH 011 Jgl l R R H In the above formula n represents a small whole number varying from 1 to 6, 7 or 8, or more, up to probably or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i. e., It varies from 1 to 4; R represents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to carbon atoms, such as a butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

Because a resin is organic solvent-soluble does not mean it is necessarily soluble in any organic solvent. This is particularly true where the resins are derived from trifunctional phenols as previously noted. However, even when obtained from a difunctional phenol, for instance, paraphenylphenol, one may obtain a resin which is not soluble in a nonoxygenated solvent, such as benzene, or xylene, but requires an oxygenated solvent such as a low molal alcohol, dioxane, or diethyleneglycol diethylether. Sometimes a mixture of the two solvents (oxygenated and nonoxygenated) will serve. See Example 9a of U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Ke-iser.

The resins herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene 8 or benzene-soluble as described in aforementioned U. S. Patent No. 2,499,365, or in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser. In said patent there are described oxyalkylation-susceptible, fusible, nonoxygenated-organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resins having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule. These resins are difunctional only in regard to methylol-forming reactivity, are derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol, and are formed in the substantial absence of trifunctional phenols. The phenol is of the formula in which R is an aliphatic hydrocarbon radical having at least 4 carbon atoms and not more than 24 carbon atoms, and substituted in the 2,4,6 position.

If one selected a resin of the kind just described previously and reacted approximately one mole of the resin with two moles of formaldehyde and two moles of a basic nonhydroxylated secondary amine as specified, following the same idealized over-simplification previously referred to, the resultant product might be illustrated The basic nonhydroxylated amine may be designed thus:

on on on on on on H I n] n n 11 -o c o o c n n n n n R n in R n R R As has been pointed out previously, as far as the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may be exemplified thus:

R R n in which R' is the divalent radical obtained from the particular aldehyde employed to form the resin. For reasons which are obvious the condensation product obtained appears to be described'best in terms of the method of manufacture.

As previously stated the preparation of resins, the kind herein employed as reactants, is well known. See previously mentioned U. S. Patent 2,499,368. Resins can be made using an acid catalyst or basic catalyst or a catalyst having neither acid nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst itis preferably that the base be neutralized although we have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The amount may be as small as a 200th of a percent and as such as a few 10ths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one does not get a single polymer, i. e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins we found no reason for using other than those which are lowest in price and most readily available commercially. For purposes of convenience suitable resins are characterized in the following table:

Table I M01. wt Ex- R of resin ample R Position derived 1 molecule number of R from- (based on n+2) Tertiary butyl Para 3. 5 882.5

Secondary butyl Ortho 3. 5 882. 5 Tertiary amyl Para. 3. 5 959.5 Mixed secondary Ortho". 3. 5 805. 5

and tertiary amyl. Propyl Para. 3. 5 805.5 Tertiary hexyl 3. 5 1, 036. 5 Octy 3. 5 1, 190. 5 3. 5 1, 267. 5 3. 5 1, 344. 5 do 3.5 1, 498. 5 Acetalde- 3. 5 945. 5

hyde. Tertiary amyl do do 3. 5 1, 022. 5 Nony ...do do 3.5 1,330.5 Tertiary butyl do Butyral- 3. 5 1, 071.5

dehyde Tertiary amyl do o 3. 5 1,148. 5 Nonyl .do ..do 3. 5 1,456.5 Tertiary butyl do.. Propional- 3.5 1,008.5

dehyde. Tertiary amyl do 3. 6 1, 085. 5 N onyl 3. 5 1, 393. 5 Tertiary butyl 4. 2 996. 6

Tertiary amyl 4. 2 1, 083. 4 Nonyl 4.2 1,430.6 Tertiary butyl 4. 8 1, 094.4 Tertiary amyl 4. 8 1,189.6 4. 8 1, 570. 4 1. 5 604.0 1. 5 653. 1. 688.0

10 PART 3 in which R represents a monovalent alkyl, alicyclic, arylalkyl radical and may be heterocyclic in a few instancts as in the case of piperidine and a secondary amine derived from furfurylamine by methylation or ethylation, or .a similar procedure.

Another example of a heterocyclic amine, is, of course, morpholine.

The secondary amines most readily available are, of course, amines such as dimethylamine, methylethylamine, diethylamine, dipropylamine, ethylpropylamine, dibutylamine, diamylamine, dihexylamine, dioctylamine, and dinonylamine. Other amines include bis(1,3-dimethylbutyl) amine. There are, of course, a variety of primary amines which can be reacted with an alkylating agent such as dimethyl sulfate, diethyl sulfate, an alkyl bromide, an ester of sulfonic acid, etc., to produce suitable amines within the herein specified limitations. For example, one can methylate alpha-methyl-benzylamine, or beuzylamine itself, to produce a suitable reactant. Needless to say, one can use secondary amines such as dicyclohexylamine, dibutyla-mine or amines containing one cyclohexyl group and one alkyl group, or one benzyl group and one alkyl group, such as ethylcyclohexyl amine, ethylbenzylamine, etc.

Another class of amines which are particularly desirable for the reason that they introduce a definite hydrophile effect by virtue of an ether linkage, or repetitious ether linkage, are certain basic polyether amines of the formula [R(OOnH2n)z]m l 'lm in which x is a small whole number having a value of 1 or more, and may be as much as 10 or 12; n is an integer having a value of 2 to 4, inclusive; m represents the numeral 1 to 2; and m represents a number 0 to 1, with the proviso that the sum of in plus m equals 2; and R has its prior significance, particularly as a hydrocarbon radical. Typical examples are:

Other somewhat similar secondary amines are those of the composition RO (CH2)3 as described in U. S. Patent No. 2,375,659, dated May 8, 1945, to Jones et al. In the above formula R may be methyl, ethyl, propyl, amyl,'octyl, etc.

Other amines can be obtained from products which are sold in the open market, such as may be obtained by alkylation of cyclohexylmethylamine or the alkylation of similar primary amines, or, for that matter, amines of the kind described in U. S. Patent No. 2,482,546, dated September 20, 1949, to Kaszuba, provided there is no negative group or halogen attached to the phenolic nucleus. Examples include the following: beta-phenoxyethylamine, gamma-phenoxypropylamine, beta-phenoxyalpha-methylethylamine, and beta-phenoxypropylamine.

Other suitable amines are the kind described in British Patent No. 456,517 and may be illustrated by:

PART 4 1 The products obtained by the herein described processes employed in the manufacture of the condensation product represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is difficult to actually depict the final product of the cogeneric mixture except in terms of the process itself.

A convenient piece of equipment for preparation of these cogeneric mixtures in a resin pot of the kind described in aforementioned U. S. Patent No. 2,499,368. In most instances the resin selected is not apt to be a fusible liquid at the early or low temperature stage of reaction if employed as subsequently described, in fact, usually it is apt to be a solid at ordinary or higher temperatures, for instance, ordinary room temperature. Thus, we have found it convenient to use a solvent and particularly one which can be removed readily at a cornparatively moderate temperature, for instance, at 150 C. A suitable solvent is usually benzene, xylene, or a comparable petroleum hydrocarbon or a mixture of such or similar solvents. Indeed, resins which are not soluble except in oxygenated solvents or mixtures containing such solvents are not here included as raw materials. The reaction can be conducted in such a way that the initial reaction, and perhaps the bulk of the reaction, takes place in a polyphase system. However, if desirable, one can use an oxygenated solvent such as a low-boiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher a1- cohols can be used or one can use a comparatively nonvolatile solvent such as dioxane or the diethylether of ethyleneglycol. One can also use a mixture of benzene or xylene and such oxygenated solvents. Note that the use of such oxygenated solvent is not required, in the sense that it is not necessary to use an initial resin which is soluble only in an oxygenated solvent as just noted, and it is not necessary to have a single phasesystem for reaction.

Actually, water is apt to be present as a solvent for the reason that in most cases aqueous formaldehyde is employed which may be the commercial product which is approximately 37%, or it may be diluted down to about 30% formaldehyde. However, paraformaldehyde can be used but it is more diflicult perhaps to add a solid material instead of the liquid solution and, everything else being equal, the latter is apt to be more economical. In any event, water is present as water of reaction. If the solvent is completely removed at the end of the process, no problem is involved if the material is used for any subsequent reaction. However, if the reaction mass is going to be subjected to some further reaction where the solvent may be objectionable, as in the case of ethyl or hexyl alcohol, and if there is to be subsequent oxyalkylation, then, obviously, the alcohol should not be used or else it should be removed. The fact that an oxygenated solvent need not be employed, of course, is an advantage for reasons stated. I

The products obtained, depending on the reactants se lected, may be water-insoluble or water-dispersible, or water-soluble, or close to being water-soluble. Water solubility is enhanced, of course, by making a solution in the acidified vehicle such as a dilute solution, for instance, a 5% solution of hydrochloric acid, acetic acid, hydroxyacetic acid, etc.

We have found no particular advantage in using a low temperature in the early stage of the reaction because, and for reasons explained, this is not necessary although it does apply in some other procedures that,

in a general way, bear some similarity to the present procedure. There is no objection, of course, to giving the reaction an opportunity to proceed as far as it will at some low temperature, for instance, 30 to 40 but ultimately one must employ the higher temperature in order to obtain products of the kind herein described. If a lower temperature reaction is used initially the period is not critical, in fact, it may be anything from a few hours up to 24 hours. We have not found any case where it was necessary or even desirable to hold the low temperature stage for more than 24 hours. In fact, we are not convinced there is any advantage in holding it at this stage for more than 3 or 4 hours at the most. This, again, is a matter of convenience largely for one reason. In heating and stir-ring the reaction mass there is a tendency for formaldehyde to be lost. Thus, if the reaction can be conducted at a lower temperature so as to use up part of the formaldehyde at such lower temperature, then the amount of unreacted formaldehyde is decreased subsequently and makes it easier to prevent any loss. Here, again, this lower temperature is not necessary by virtue of heat convertibility as previously referred to.

If solvents and reactants are selected so the reactants and products of reaction are mutually soluble, then agitation is required only to the extent that it helps cooling or helps distribution of the incoming formaldehyde. This mutual solubility is not necessary as previously pointed out but may be convenient under certain circumstances. On the other hand, if the products are not mutually soluble then agitation should be more vigorous for the reason that reaction probably takes place principally at the interface and the more vigorous the agitation the more interfacial area. The general procedure employed is invariably the same when adding the resin and the selected solvent, such as benzene or xylene. Refluxing should be long enough to insure that the resin added, preferably in a powdered form, is completely dissolved. However, if the resin is prepared as such it may be added in solution form, just as preparation is described in aforementioned U. S. Patent 2,499,368. After the resin is in complete solution the amine is added and stirred. Depending on the amine selected, it may or may not be soluble in the resin solution. If it is not soluble in the resin solution it may be soluble in the aqueous formaldehyde solution. If so, the resin then will dissolve in the formaldehyde solutionas added, and if not, it is even possible that the initial reaction mass could be a threephase system instead of a two-phase system although this would be extremely unusual. This solution, or mechanical mixture, if not completely soluble is cooled to at least the reaction temperature or somewhat below, for example 35 C. or slightly lower, provided this initial low temperature stage is employed. The formaldehyde is then added in a suitable form. For reasons pointed out we prefer to use a solution and whether to use a commercial 37% concentration is simply a matter of choice. In large scale manufacturing there may be some advantage in using a 30% solution of formaldehyde but apparently this is not true on a small laboratory scale or pilot plant scale. 30% formaldehyde may tend to decrease any formaldehyde loss or make it easier to control unreacted formaldehyde loss.

Returning again to the preferred method of reaction and particularly from the standpoint of laboratory procedure employing a glass resin pot, when the reaction has proceeded as far as one can reasonably expect at a low temperature; for instance, after holding the reaction mass with or without stirring, depending or whether or not it is homogeneous, at 30 or 40 C. for 4 or 5 hours, or at the most, up to lO-24 hours, we then complete the reaction by raising the temperature up to C., or thereabout as required. The initial low temperature procedure can be eliminated or reduced to merely the shortest period of time which avoids loss of amine or formaldehyde. At a higher temperature we use a phase-separating trap and subject the mixture to reflux condensation until the water of reaction and the water of solution of the formaldehyde is eliminated. We then permit the temperature to rise to somewhere about 100 0., and generally slightly above 100 C., and below 150 C., by eliminating the solvent or part of the solvent so the reaction mass stays within this predetermined range. This period of heating and refluxing, after the water is eliminated, is continued until the reaction mass is homogeneous and then for one to three hours longer. The removal of the solvents is conducted in a conventional manner in the same way as the removal of solvents in resin manufacture as describe in aforementioned U. S. Patent No. 2,499,368.

Needless to say, as far as the ratio of reactants goes we have invariablyemployed approximately one mole of the resin based on the molecular weight of the resin molecule, 2 moles of the secondary amine and 2 moles of the formaldehyde. In some instances we have added a trace of caustic as an added catalyst but have found no particular advantage in this. In other cases we have used a slight excess of formaldehyde and, again, have not found any particular advantage in this. In other cases we have used a slight excess of amine and, again, have not found any particular advantage in so doing. Whenever feasible we have checked the completeness of reaction in the usual ways, including the amount of Water of reaction, molecular weight, and particularly in some instances, have checked whether or not the end-product showed surfaceactivity, particularly in a dilute acetic acid solution. The nitrogen content after removal of unreacted amine, if any is present, is another index.

In light of what has been said previously, little more need be said as to the actual procedure employed for the preparation of the herein described condensation products. The following example will serve by way of illustration.

Example 1b The phenol-aldehyde resin is the one that has been identified previously as Example 2a. It was obtained from a para-tertiary butylphenol and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. This corresponded to an average of about 3 /2 phenolic nuclei, as the value for n which excludes the two external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4 nuclei, excluding the two external nuclei or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a light amber color.

882 grams of the resin identified as 2a, preceding, were powdered and mixed with an equal weight of xylene, i. e., 882 grams. The mixture was refluxed until solution was complete. It was then adjusted to approximately 30 C. to 35 C., and 146 grams of diethylamine added. The mixture was stirred vigorously and formaldehyde added slowly. The formaldehyde was used as a 37% solution and 162 grams were employed, which was added in about 2 hours. The mixture was stirred vigorously and kept within a temperature range of 30 to 45 C. for about 20 hours. At the end of this period of time it was refluxed, using a phase-separating trap and a small amount of aqueous distillate Withdrawn from time to time, and the presence of unreacted formaldehyde noted. Any unreacted formaldehyde seemed to disappear within 2 to 3 hours after refluxing was started. As soon as the odor of formaldehyde was no longer detectible the phaseseparating trap was set so as to eliminate all water of solution and reaction. After the water was eliminated part of the xylene was removed until the temperature reached approximately 145 C., or slightly higher. The mass was kept at this higher temperature for about 4 hours and reaction stopped. During this time any additional water, which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in the cogeneric mixture. A small amount of the sample was heated on a water bath to remove the excess xylene and the residual material was dark red in color and had the consistency of a sticky fluid or tacky resin. The overall time for the reaction was about 30 hours. Time can be reduced by cutting low temperature period to approxmately 3 to 6 hours.

Note that in Table II following there are a large number of added examples illustrating the same procedure. In each case the initial mixture was. stirred and held at a fairly low temperature (30 to 40 C.) for a period of several hours. Then refluxing was employed until the odor of formaldehyde disappeared. After the odor of formaldehyde disappeared the phase-separating trap was employed to separate out all the water, both the solution and condensation. After all the water had been separated enough xylene was taken out to have the final product reflux for several hours somewhere in the range of 145 to 150 C., or thereabouts. Usually the mixture yielded a clear solution by the time the bulk of the water, or all of the Water, had been removed.

Note that as pointed out previously, this procedure is illustrated by 24 examples in Table II.

Table II Strength of Reac- Reac- Max. Ex. Resin Amt, Amine used and amount formalde- Solvent used tion tlon distill. N0. used grs. hyde soln. and amt. temp., time, temp,

and amt. 0. hrs. C.

882 Diethylamine, 146 grams 37%, 162 g... Xylene, 882 g. 20-25 30 150 480 Dlethylamme, 73 grams 37%, 81 g Xylene, 480 g- 22-30 24 152 633 do 30%, g... Xylene, 633 g 21-24 38 147 441 Dibutylamlne, 129 grams 37%, 81 g. Xylene, 441 g- 25-37 32 149 480 do do Xylene, 480 g. 20-24 35 149 633 do do Xylene, 633 g. 18-23 24 150 882 Morpholme, 174 grams" 37%, 162 g... Xylene, 882 gm. 20-26 35 145 480 Morpholtne, 87 grams. 81 g. Xylene, 480 g- 19-27 24 156 633 do Xylene, 633 g 20-23 24 147 473 Dloetylamine (d1-2-ethylhexyla1uine), 117 grams 30%, 100 g... Xylene, 473 g 20-21 38 148 511 do do Xylene, 511 g-.. 19-20 30 145 665 do 37%, 81 g Xylene, 665 g 20-26 24 150 441 (CzH5OC2H4OCzH4hNH, 250 grams--. 30%, 100 g, Xylene, 441 g.-. 20-22 31 147 480 (CzH5OCzH4OC2H4)2NH, 250 grams d0 Xylene, 480 g 20-24 36 148 595 (O H OC2H40C4HmNH, 250 grams Xylene, 595 g. 23-28 25 145 441 (041190OH OH (CH3)0(GH3)OHCH1)2NH, 361 grams Xylene, 441 g. 21-23 24 151 480 (0 11 0 CH GH (CH3) 0 (CH3) OHCHmNH, 361 grams Xylene, 480 g. 1 20-24 24 150 511 (041190 GH OH(CH3)O(OHa)CHOHz)zNH, 361 grams Xylene, 511 g 20-22 25 146 498 (CHsOCHzCHgOCHzCHOCHzCHzhNH, 309 grams. Xylene, 498 g 20-25 24 542 (C1130CH OHgOOH OH OOHzCHmNH, 309 grams. Xylene, 542 g- 28-38 30 142 547 (CH3OCH2CHZOCH2CH2OCH2CH2)2NH, 309 grams Xylene, 547 g 25-30 26 148 441 (CHsOOHgCHgCHzCHzOHgCHzMNH, 245 grams do Xylene, 441 g. 20-22 28 143 595 (CH3OCHzCHgOHzCHzCHzCHzMNH, 245 grams 30%, 100 g... Xylene, 595 g 18-20 25 146 391 (CHSOOH20H2OH2OH2CH2OH2)2NH, 98 grams 30%, 50 g. Xylene, 391 g 19-22 24 PART 5 Example 1c The oxyalkylation-susceptible compound employed is the one previously described and designated as Example lb. Condensate lb was in turn obtained from diethylamine and the resin previously identified as Example 2a. Reference to Table I shows that this particular resin is obtained from paratertiarybutylphenol and formaldehyde. 10.56 pounds of this resin condensate were dissolved in 8.8 pounds of solvent (xylene) along with one pound of finely powdered caustic soda as a catalyst. Adjustment was made in the autoclave to operate at a temperature of approximately 125 C. to 130 C., and at a pressure of about to pounds.

The time regulator was set so as to inject the ethylene oxide in approximately three hours and then continue stirring for a half-hour or longer. The reaction went readily and, as a matter of fact, the ethylene oxide could have been injected in less than an hours time and probably the reaction could have been completed without allowing for a subsequent stirring period. The speed of reaction, particularly at the low pressure, undoubtedly was due in a large measure to excellent agitation and also to the comparatively high concentration of catalyst. The amount of ethylene oxide introduced was equal in weight to the initial condensation product, to wit, 10.56 pounds. This represented a molal ratio of 24 moles of ethylene oxide per mole of condensate.

The theoretical molecular weight at the end of the reaction period was 2112. A comparatively small example, less than 50 grams, was withdrawn merely for examination as far as solubility or emulsifying power was concerned and also for the purpose of making some tests on various oil-field emulsions. The amount withdrawn was so small that no cognizance of this fact is included in the data, or subsequent data, or in the data presented in tabular form in subsequent Tables HI and IV.

The size of the autoclave employed was 25 gallons. In innumerable comparable oxyalkylations we have withdrawn a substantial portion at the end of each step and continued oxyalkylation on a partial residual sample. This was not the case in this particular series. Certain examples were duplicated as hereinafter noted and subjected to oxyalkylation with a different oxide.

Example 20 This example simply illustrates the further oxyalkylation of Example 1c, preceding. As previously stated, the oxyalkylation-susceptible compound, to wit, Example 1!), present at the beginning of the stage was obviously the same as at the end of the prior stage (Example 10), to wit, 10.56 pounds. The' amount of oxide present in the initial step was 10.56 pounds, the amount of catalyst remained the same, to wit, one pound, and the amount of solvent remained the same. The amount of oxide added was another 10.56 pounds, all addition of oxide in these various stages being based on the addition of this particular amount. Thus, at the end of the oxyethylation step the amount of oxide added was a total of 21.12 pounds and the molal ratio of ethylene oxide to resin condensate was 48 to 1. The theoretical molecular weight was 31.68.

The maximum temperature during the operation was 125 C. to 130 C. The maximum pressure was in the range of 15 to 20 pounds. hours.

The time period was 3 /2 Example 30 The oxyalkylation proceeded in the same manner described in Examples 10 and 2c. There was no added solvent and no added catalyst. The oxide added was 10.56 pounds and the total oxide in at the end of the oxyethylation step was 31.68 pounds. The molal ratio of oxide to condensate was 72 to 1. Conditions as far as temperature and pressure and time were concerned were all the same as in Examples 10 and 2c. The time period, as in Examples 10 and 20, was 3 /2 hours.

Example 4c The oxyethylation was continued and the amount of oxide added again was 10.56 pounds. There was no added catalyst and no added solvent. The theoretical molecular weight at the end of the reaction period was 5280. The molal ratio of oxide to condensate was 96 to 1. Conditions as far as temperature and pressure were concerned were the same as in previous examples. The time period was slightly longer, to wit, 4 hours. The reaction unquestionably began to slow up somewhat.

Example 5c The oxyethylation continued with the introduction of another 10.56 pounds of ethylene oxide. No added solvent was introduced and, likewise, no added catalyst was introduced. The theoretical molecular weight at the end of the agitation period was 6336, and the molal ratio of oxide to resin condensate was 124 to l. The time period, however, had increased to 5 hours, even though the operating temperature and pressure remained the same as in previous examples.

Example 60 The same procedure was followed as in the previous examples except that an added A pound of powdered caustic soda was introduced to speed up the reaction. The amount of oxide added was another 10.56 pounds, bringing the total oxide introduced to 63.36 pounds. The temperature and pressure during this period were the same as before.

Notwithstanding the addition of added caustic the time required for the oxyethylation was 5 hours. There was no added solvent.

Example 7c The same procedure was followed as in the previous six examples without the addition of morecaustic or more solvent. The total amount of oxide introduced at the end of the period was 72.93 pounds. The theoretical molecular weight at the end of the oxyalkylation period was 8448. The time required for the oxyethylation was a bit longer than in the previous step, to wit, 6 hours.

Example This was the final oxyethylation in this particular series. There was no added solvent and no added catalyst. The total amount of oxide added at the end of this step was 85.48 pounds. The theoretical molecular weight was 9604. The molal ratio of oxide to resin condensate was 192. Conditions as far as temperature and pressure were concerned were the same as in the previous examples and the time required for oxyethylation was the same as in Example 70, preceding, to wit, 6 hours.

The same procedure as described in the previous examples was employed in connection with a number of the other condensates described previously. All these data have been presented in tabular form in a series of four tables, Tables III and 1V, V and VI.

In substantially every case a 25-gallon autoclave was employed, although in some instances the initial oxyethylation was started in a 15-gallon autoclave and then transferrcd to a 25-gallon autoclave. This is immaterial but The example number of each compound is indicated in the first column.

The identity of the oxyalkylation-st]sceptible compound, to wit, the resin condensate, is indicated in the second column.

The amount of condensate is shown in the third column.

Assuming that ethylene oxide alone is employed, as happens to be the case in Examples through 400, the amount of oxide present in the oxyalkylation derivative is shown in column 4, although in the initial step since no oxide is present there is a blank.

When ethylene oxide is used exclusively the 5th column is blank.

The 6th column shows the amount of powdered caustic soda used as a catalyst, and the 7th column shows the amount of solvent employed.

The th column shows the theoretical molecular weight at the end of the oxyalkylation period.

The 8th column states the amount of condensate present in the reaction mass at the end of the period.

As pointed out previously, in this particular series the amount of reaction mass withdrawn for examination was so small that it was ignored and for this reason the resin condensate in column 8 coincdes with the figure in column 3.

Column 9 shows the amount of. ethylene oxide employed in the reaction mass at the end of the particular period.

Column 10 can be ignored insofar that no propylene oxide was employed.

Column 11 shows the catalyst at the end of the reaction period.

Column 12 shows the amount of solvent at the end of the reaction period.

Column 13 shows the molal ratio of ethylene oxide to condensate.

Column 14 can be ignored for the reason that no propylene oxide was employed.

Referring now to Table VI. It is to be noted that the first column refers to Examples 1c, 20, 3c, etc.

The second column gives the maximum temperature employed during the oxyalkylation step and the third column gives the maximum pressure.

The fourth column gives the time period employed.

The last three columns show solubility tests by shaking a small amount of the compound, including the solvent present, with several volumes of water, xylene and kerosene. It sometimes happens that although xylene in comparatively small amounts will dissolve inthe con-.

centrated material, when the concentrated material in turn is diluted with xylene, separation takes place.

Referring to Table IV, Examples 41c through 800 are the counterparts of Examples 10 through 400, except that the oxide employed is propylene oxide instead of ethylene oxide. Therefore, as explained previously, two columns are blank, to wit, columns 4 and 9.

Reference is now made to Table V. It is to be noted these compounds are designated by d numbers, 1d, 2d, 3d, etc., through and including 32d. They are derived, in turn, from compounds in the 0 series, for example, 35c, 39c, 53c and 620. These compounds involve the use of both ethylene oxide and propylene oxide. Since compounds 1c through 40c were obtained by the use of ethylene oxide, it is obvious that those obtained from 350, through 39c, involve the use of ethylene oxide first,

18 and propylene oxide afterward. Inversely, those compounds obtained from 53c and 620 obviously came from a prior series in which propylene oxide was used first.

In the preparation of this series indicated by the small letter d, as ld, 2a, 3d, etc., the initial c series such as 350, 39c, 53c, and 620, were duplicated and the oxyalkylation stopped at the point designated instead of being carried further as may have been the case in the original oxyalkylation step. Then oxalkylation proceeded by using the second oxide as indicated by the previous explanation, to wit, propylene oxide in 1d through 16d, and ethylene oxide in 17d through 32d, inclusive.

In examining the table beginning with 1d, it will be noted that the initial product, i. e., 350, consisted of the reaction product involvingfl0.5 pounds of the resin condensate, 15.84 pounds of ethylene oxide, 1.0 pound of caustic soda, and 8.8 pounds of the solvent.

It is to be noted that reference to the catalyst in Table V refers to the total amount of catalyst, i. e. the catlyst present from the first oxyalkylation step plus added catalyst, if any. The same is true in regard to the solvent. Reference to the solvent refers to the total solvent present, i. e., that from the first oxyalkylation step plus added solvent, if any.

In this series, it will be noted that the theoretical molec ular weights are given prior to the oxyalkylation step and after the oxyalkylation step, although the value at the end of one step is the value at the beginning of the next step, except obviously at the very start the value depends on the theoretical molecular weight at the end of the initial oxyalkylation step; i. e., oxyethylation for 14! through and oxypropylation for 17d through 32d.

It will be noted also that under the molal ratio the values of both oxides to the resin condensate are included.

The data given in regard to the operating conditions is substantially the same as before and appears in Table VI.

The products resulting from these procedures may contain modest amounts, or have small amounts, of the solvents as indicated by the figures in the tables. If desired the solvent may be removed by distillation, and particularly vacuum distillation. Such distillation also may remove traces or small amounts of uncombined oxide, if present and volatile under the conditions employed.

Obviously, in the use of ethylene oxide and propylene oxide in combination one need not first'use one oxide and then the other, but one can mix the two oxides and thus obtain what may be termed an indifferent oxyalkylation, i. e., no attempt to selectively add one and then the other, or any other variant.

Needless to say, one could start with ethylene oxide and then use propylene oxide, and then go back to ethylene oxide; or, inversely, start with propylene oxide, then use ethylene oxide, andthen go back to propylene oxide; or, one could use a combination in which butylene oxide is used along with either one of the two oxides just mentioned, or a combination of both of them.

The colors of the product s usually vary from a reddish amber tint to a definitely red, and amber. The reason is primarily that no effort is made 'to obtain colorless resins initially and the resins themselves may be yellow, amber, or even dark amber. Condensation of a nitrogenous product invariably yields a darker product than the original resin and usually has ajreddish color. The solvent employed, if xylene, adds nothing to the colorbut one may use a darker colored aromatic petroleum solvent. oxyalkylation generally tends to yield lighter colored products and the more oxide employed the lighter the color of the product. Products can be prepared in which the final color is a lighter amber with a reddish tint. Such products can be decolorized by the use of clays, bleaching chars, etc. As far as use in demulsification is concerned, or some other industrial uses,

is the case for the reason that if one adds hydrochlorie acid, for example, to neutralize the alkalinity one may partially neutralize the basic nitrogen radical. also. The preferred procedure is to ignore the presence of the alkali unless it is objectionable or else add a stoichiometric amount of concentrated hydrochloric acid equal to the caustic soda present.

Table III Composition before Composition at end Molal rotlo Molec. Ex. No. wt.

-8 0-8 Ethl. Propl. Cata- Sol- 0-8 Ethl. Propl. 0861- S01- Ethyl. Pmpl. based cm d., cmpd., oxide, oxide, lyst, vent, crnpd., oxide, oxide, lyst, vent, oxide oxide on theex. 0. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. to oxyto oxyoreticol alkyl. alkyl value suscept. suscept.

cmpd. cmp

10. 56 1. 0 8. 8 10. 56 10. 56 1. 0 8. 8 24 10. 56 10. 56 1. 0 8. 8 10. 56 21. 12 1. 0 8. 8 48 10. 56 21. 12 1. 0 8. 8 10. 56 31. 68 1. 0 8.8 72 10. 56 31. 68 1. 0 8.8 10.56 42. 24 1. 0 8. 8 96 10. 56 42. 24 1. 0 8.8 10. 56 52. 80 1. 0 8. 8 124 10. 56 52. 80 1. 25 8.8 10.56 63. 36 1. 25 8. 8 144 10.56 63. 36 1. 25 8. 8 10. 56 73. 92 1. 25 8. 8 168 10. 66 73. 92 1. 25 8. 8 10. 56 85. 48 1. 25 8. 8 192 12.56 1. 0 9. 6 12. 56 12.56 1. 0 9. 6 28. 6 12. 56 12. 56 1. 0 9. 6 12. 56 25. 12 1. 0 9. 6 57. 2 12.56 25.12 1. 0 9. 6 12.56 37. 68 1. 0 9. 6 85.8 12.56 37. 68 1. 0 9. 6 12.56 50. 24 1. 0 9. 6 114. 4 12. 56 50. 24 1. 0 9. 6 12. 56 62. 80 1. 6 9. 6 143.0 12. 56 62. 80 1. 5 9. 6 12. 56 75. 36 1. 5 9. 6 171. 6 12. 56 75. 63 1. 5 9. 6 12. 56 87.92 1. 5 9. 6 200. 2 12. 56 87. 92 1. 5 9. 6 12. 56 100. 48 1. 5 0. 6 228. 8 10. 82 1. 0 8.8 10.84 10. 84 1.0 8. 8 24. 6 10.84 10. 84 1. 0 8. 8 10.84 21. 68 1. 0 8. 8 49. 2 10. 84 21. 68 1. 0 8. 8 10. 84 32. 52 1. 0 8.8 73. 8 10. 84 32. 52 1. 0 8. 8 10. 84 43. 36 1. 0 8. 8 98. 4 10.84 43. 36 1. 0 8. 8 10.84 54. 2O 1. 0 8.8 123. 0 10. 84 54. 1. 8. 8 10.84 65. 04 1. 25 8. 8 147. 6 10. 84 65. 04 1. 25 8. 8 10. 84 75. 88 1. 25 8. 8 172. 2 10. 84 75.88 1. 25 8. 8 10. 84 86. 72 1. 25 8.8 196. 8 12.84 1. 0 10.2 12. 84 12.84 1. O 10.2 29. 2 12. 84 12. 84 1. 0 10. 2 12. 84 25. 68 1. 0 10. 2 58. 4 12. 84 25. 68 1. 0 16. 2 12. 84 38. 52 1. 0 10.2 87. 6 12. 84 38. 52 1. 0 10. 2 12. 84 51.36 1. 0 10.2 116. 8 12. 84 51. 36 1. 0 10.2 12.84 64. 20 1. 0 10. 2 146.0 12.84 64. 20 1. 5 10.2 12.84 77. 04 1. 5 10. 2 175. 2 12. 84 77. 04 1. 5 10.2 12. 84 89. 88 1. 5 10. 2 204. 4 12.84 89.88 1. 5 10.2 12. 84 102. 72 1. 5 10.2 233. 6 16. 56 1. 0 8; 8 10.56 5. 28 1. 0 8. 8 12 10.56 5.28 1. 0 8. 8 10.56 10. 56 1.0 8.8 24 l 10.56 10. 56 1. 0 8. 8 10. 56 15. 84 1. 0 8.8 36 10. 56 15. 84 1. 0 8. 8 10. 56 21. 12 1. O 8. 8 48 10. 56 21.12 1. 0 8. 8 10.56 26. 1. 0 8. 8 60 10.56 26. 40 1. 0 8. 8 10.56 31. 68 1. 0 8. 8 72 10. 56 31. 68 1. 0 8. 8 10.56 36. 96 1. 0 8.8 84 40c 16 16. 56 36. 96 1. 0 8. 8 10. 56 2. 24 1. 6 8. 8 96 Oxyalkylatlon-susoeptiblo.

Table IV Composition before Composition at end Molal ratio Molec. Ex. No. 7 wt.

0-8 0-8 Ethl. Propl. Cata- 801- 0-8 Etbl. Propl. Cata- Sol- Ethyl. Propl. based ompd., cmpd., oxide, oxide, lyst, vent, cmpd., oxide, oxide, lyst, vent, oxide oxide on theex. No. lbs. lbs. lbs. lbs. lbs. lbs. lbs. 8. lbs. lbs. to oxyto oxyoretical alkyl. alkyl. vnlue suscept. suscept. cmp cmpd.

10.56 1. 0 8.8 10.56 10.56 1. 0 8. 8 18. 2 2,112 10. 56 10.56 1. 0 8.8 10. 56 21. 12 1. O 8. 8 36. 4 3,168 10. 56 21. 12 1. 0 8. 8 10.56 21.68 1. 0 8.8 54. 6 4, 224 10. 56 31. 68. 1. 0 8.8 10. 56 42. 24 1. 0 8. 8 72. 8 5. 280 10. 56 42. 24 1. 0 8. 8 10. 56 52. 1. 0 8. 8 91. 0 6, 336 10.56 52. 80 1. 5 8. 8 10. 56 73.92 1. 5 8. 8 127. 4 8, 348 10. 56 73. 92 1. 5 8. 8 10. 56 95. 04 1. 5 8. 8 163. 8 10, 560 10.56 95. 04 1. 5 8. 8 10. 56 116. 16 1. 5 8. 8 200. 2 12, 672 12. 56 1. 2 9. 6 12.56 12.56 1. 2 9. 6 21.6 2, 512 12. 56 12.56 1. 2 9. 6 12. 56 25. 12 1. 2 9. 6 43. 2 3, 768 12. 56 25. 12 1. 2 9. 6 12. 56 37. 68 1.2 9. 6 64. 8 5, 024 12. 56 37. 68 1. 2 9. 6 12. 56 50. 24 1. 2 9. 6 86. 4 6, 280 12. 56 50. 24 1. 2 9. 6 12. 56 62. 80 1. 2 9.6 108.0 7, 836 12.56 62. 80 1. 2 9. 6 12. 56 87. 92 1. 2 9. 6 151. 2 10, 048 12. 56 87. 92 1. 2 9. 6 12. 56 113. 04 1. 2 9. 6 194. 8 12, 560 12.56 113. 04 1. 2 9. 6 12. 56 138.16 1. 2 9. 6 238. 2 15,072 10. 84 1. 0 8. 8 10.84 10.84 1. 0 8. 8 18. 7 2, 168 10. 84 10 84 i 1. 0 8. 8 10. 84 21. 68 1. 0 8. 8 37. 4 3, 252 10. 84 21.68 1. 0 8. 8 10.84 32. 52 1. 0 8. 8 56.1 4, 336 10. 84 32. 52 1. 0 8. 8 10. 84 43. 36 1. 0 8. 8 74. 8 5, 426 10. 84 43. 36 1. 0 8. 8 10. 84 54. 20 1. 0 8. 8 93. 5 6. 504 10. 84 54. 20 1. 0 8.8 10. 84 75. 88 1. 0 8. 8 130. 9 8, 672 10. 84 75. 88 1. O 8. 8| 10. 84 97, 56 1. 0 8. 8 170. 3 10 840 See footnote at end of table.

Table Vl-Contmued Max. Max. Solubility Ex. temp., pres., Time, No. G. p. s. 1. hrs.

Water Xylene Kerosene 15-20 6 Soluble 15-20 4 Insoluble 15-20 3 Emulslfiebleu 15-20 3 Soluble 15-20 4 15-20 4 15-20 3 15-20 3 15-20 4 5-10 2 Insluble -10 2 Emulslfisble 5'10 2% Snlnhla 5-10 3 5-10 4 5-10 3 5-10 4 5-10 5 -15 10-15 10-15 lO- 10-15 10-15 10-15 10-15 10-15 Insoluble. 10-15 Dlsperslble. 10-15 D0. 10-15 Soluble. 10-15 D0. 10-15 D0. 10-15 D0. 10-15 D0.

5-10 Insoluble 5-10 D0. 5-10 Dlsperslble. 5-10 Soluble. 5-10 Do. 5-10 D0. 5-10 Do. 5-10 Do. 5-10 Insoluble. 5-10 Do. 5-10 Dlsperslble. 5-10 Soluble. 5-10 Do. 5-10 D0. 5-10 Do. 5-10 Do. 10-15 Insoluble. 10-15 D0. 10-15 Dlsperslble 10-15 Do. 10-15 Soluble. 10-15 Do. 10-15 Do. 10-15 Do. 15 Insoluble. 15-20 Do. 15-20 Do. 15-20 Dispersible 15-20 D0- 15 20 Soluble. 15-20 0. 15-20 1520 Insoluble. 15-20 15-20 15-20 15-20 15-20 15-20 15-20 20-25 D0. 20-25 Do. 20-25 Do. 20-25 20-25 Do. 20-25 Do.

20-25 Do. 20-25 Do. 20-25 Soluble. 2045 Do. 20-25 D0. 20-25 Dov 20-25 Do. 20-25 Do. 20-25 D0. 20-25 Do. 20-30 Do. 20-30 0. 20-30 Dlsperslble. 20-30 Insoluble. 20-30 D 20-30 20-30 D0;

' to soluble. 20-30 5 Soluble Do.

PART 6 The f"me'tliate"reactants are strongly basic. Initial oiyalkyla- 15 tion of these products with a monoepoxide or diepoxide 25 can be accomplished generally, at least in the initial stage, without the addition of the usual alkaline catalyst such as those described in connection with oxyalkylation employing monoepoxides in Part immediately-preceding. As a matter of fact, the procedure is substantially the same as using a non-volatile monoepoxide such as glycide or methylglycide. However, during progressive oxyalklyation with a monoepoxide it is usually necessary to use a catalyst as previously described and, thus, there may or may not be suflicient catalyst present for the reaction with the diepoxide. Reference to the catalyst present includes the residual catalyst remaining from the oxyalkylation step in which the monoepoxide was used.

Briefly stated then, employing polyepoxides in combination with a nonbasic reactant the usual catalysts include alkaline materials, such as caustic soda, caustic potash, sodium methylate, etc. Other catalysts may be acidic in nature and are of the kind illustrated by iron and tin chloride. Furthermore, insoluble catalysts such as clay or specially prepared mineral catalysts have been used. If for any reason the reactiondoes not proceed rapidly enough with the diglycidyl ether or other analogous reactant then a small amount of finely divided caustic soda or sodium methylate can be employed as a catalyst. The amount generally employed would be 1% or 2%.

It goes without saying that the reaction can take place in an inert solvent, i. e., one that is not oxyalkylationsusceptible. Generally speaking, this is most conveniently an aromatic solvent such as xylene or a higher boiling coal tar solvent, or else a similar high boiling aromatic solvent obtained from petroleum. One can employ an oxygenated solvent such as the diethylether of ethyleneglycol, or the diethylether or propyleneglycol, or similar ethers, either alone or in combination with a hydrocarbon solvent. The selection of the solvent depends in part on the subsequent use of the derivatives or reaction products. If the reaction products are to be rendered solvent-free and it is necessary that the solvent be readily removed as, for example, by the use of vacuum disillation, then xylene or an aromatic petroleum solvent will serve. If the product is going to be subjected to oxyalkylation subsequently, then the solvent should be one which is not oxyalkylation-susceptible. It is easy enough to select a suitable solvent if required in any instance but, everything else being equal, the solvent chosen should be the most economical one.

Example 1e amine and resin 2a; resin 2a, in turn, was obtained from para-tertiarybutylphenol and formaldehyde.

In any event, 317 grams of the oxyalkylated resin condensate previously identified as 20 were dissolved in' approximately an equal weight of xylene. About 3 grams of sodium methylate were added as a catalyst so the total amount of catalyst present, including residual catalyst from the prior'oxyalkylation, was about 3.4 grams. 18 grams of diepoxide A were mixed with an equal weight of xylene. The initial addition of the diepoxide solution was made after raising the temperature of the reaction mass to about 107 C. The diepoxide was added slowly over a period of one hour. During this time the temperature was allowed to rise to about 129 C. The mixture was allowed to reflux at about 138 C. using a phase-separating trap. A small amount of xylene was removed by means of a phase-separating trap so the refluxing temperature rose gradually to about 175 C. The mixture was refluxed at this temperature for about 5 hours. At the end of this period the xylene which had been removed by means of the phase-separating trap was returned to the mixture. A small amount of material was withdrawn and the xylene evaporated on a hot plate in order to examine the physical properties. The material was an amber, or light reddish amber, viscous liquid. It was insoluble in water; it was insoluble in gluconic acid, but it was soluble in xylene and particularly in a mixture of xylene and 20% methanol. However, if the material was dissolved in an oxygenated solvent and then shaken with 5% gluconic acid it showed a definite tendency to disperse, suspend, or form a sol, and particularly in a xylene-methanol mixed solvent as previously described, with or without the further addition of a little acetone.

Generally speaking, the solubility of these derivatives is in line with expectations by merely examining the solubility of the preceding intermediates, to wit, the oxyalkylated resin condensates prior to treatment with the diepoxide. These materials, of course, vary from extremely water-soluble products due to substantial oxy ethylation, to those which conversely are water-insoluble but xylene-soluble or even kerosene-soluble due to high stage oxypropylation. Reactions with diepoxides or polyepoxides of the kind herein described reduce the hydrophile properties and increase the hydrophobe properties, i. e., generally make the products more soluble in kerosene or a mixture of kerosene and xylene, or in xylene, but less soluble in water. Since this is a general reference to solubility will be omitted.

The procedure employed, of course, is simple in light of what has been said previously and in effect is a pro- Table VII Ex. Oxy. Amt Di Amt, Catalyst Xy- Molar Time of Max. No. condengrs. epoxide grs. (N aOCHz), lene, ratio reaction, temp, Color and physical state sate used grs. grs. hrs. C.

317 A 18.5 3. 4 336 2:1 4 Reddish amber resinous mass. 264 A 9. 3 2. 7 273 2:1 4 178 D0; 251 A 18. 5 2. 7 270 2:1 4 180 D0. 314 A 9. 3 3. 2 323 2:1 4. 5 182 D0. 385 A 9. 3 3. 9 394 2: 1 4 178 D0. 317 A 18. 5 3. 4 336 2:1 4. 5 175 D0. 251 A 9. 3 2. 6 260 2:1 4. 5 180 D0. 325 A 9. 3 3. 3 334 2: l 4 180 D0. 257 A 18. 5 2. 8 276 2: 1 4 182 D0. 343 A 9. 3 3. 5 352 2:1 4 178 D0. 370 A 18. 5 3. 9 389 2: 1 4 180 D0. 269 A 9. 3 2. 8 278 2:1 4 177 D0. 317 A 9. 3 3.3 326 2:1 5 176 Do. 212 A 4. 7 2. 2 217 2:1 4 175 D0. 227 A 4. 7 2. 3 232 2:1 4 175' D0- rule which applies throughout, for sake of brevity future Table VIII Ex. Oxy. Amt, Dl- Amt, Catalyst Xy- Molar -llme of Max. No. coudengrs. epoxido grs. (NaOCHI), lene, ratio reaction, temp., Color and physical state sate used grs. grs. hrs. O.

317 B 11.0 3.3 328 2:1 4 170 Reddlsn amber resinous mass. 264 B 5. 5 2. 7 270 2:1 4 175 Do. 251 B 11. 2. 6 262 2:1 4 170 Do. 314 B 5. 3. 2 320 2: 1 4 175 Do. 385 B 5. 5 3. 9 391 2:1 4 130 Do. 317 B 11.0 3.3 328 2:1. 4 182 Do. 251 B 5.5 2.0 257 2:1 4 184 Do. 325 B 5. 5 3. 3 331 2:1 4 130 Do. 257 B 11.0 2.7 268 2:1 4 130 Do. 343 B 5. 5 3. 5 349 2:1 4 178 Do. 370 B 11. 0 3, 8 381 2:1 4 5 130 :Do. 269 B 5. 5 2.8 275 2:1 4. 5 180 D0. 317 B 5.5 3.2 323 2:1 4.5 178 Do. 212 B 2.8 2. 2 215 2:1 4. 5 175 D0. 227 B 2. 8 2. 3 230 2:1 4. 5 175 Do.

Table IX cule or the diepoxide molecule actually may vary from the true molecular weight by several percent. b The condensate can be depicted in a simplified form Oxyalkyl- AmOuntof Ammmt of which, for convenience, may be shown thus:

IgSlIl conreatgziorz product, grs. solvent m (Amine)CH (Resin)CH (Amine) 8.5%8 1 852 If such product is subjected to oxyalkylation reaction 51390 2:695 1:348 involves the phenolic hydroxyls of the resin structure 12 930 2,586 1, 293 151780 3,156 1,578 and, thus, can be deplcted 1n the followlng manner.

6,710 3,355 1,678 10.420 2, 084 1,042 (Am1ne)CH (Oxyalkylated Res1n)CH (Am1ne) 13,380 2, 676 1, 335 24, 53 5: 213 Following such simplification the reaction with a 2% polyepoxide, and particularly a diepoxide, would be 131040 2:668 1:304 deplcted thus! 17, 310 3, 462 1, 731 18, 550 3, 710 1,855

(Amine)CHz(0xyalkyla-ted Resin) CHAAmine) Table X 13.0.11.

Prob (Amine)CH(Oxyalkylnted Resin)CH1(Amine) Ex. No. Oxyalkyl. wt. of Amount of Amount of resin eonreaction product, grs. solvent densate Product 1n which D. G. E. represents a diglycldyl ether as specified. 81328 253% {319 As has been pointed out previously, the condensation 2.338 5.5 39 reacnon may produce other products, including, for

I U 2, 3,126 1,563 example, a product whlch may be indicated thus 1n light ,560 3,280 1 680 58 1:027 of what has been said previously. 1 ,2 1,654 K 5,300 2,680 1,340 [(Am1ne)CH (Res1n)] 13, 050 3, 48s 1, 744 v g'gg This product, since it is susceptible to oxyalkylation by 1 128 means of the oxyalkylated phenolic hydroxyl groups and 181400 31680 1:840 r depending on the selection of the amine, may be suscept1ble to oxyalkylatron 1n event a hydroxylated amine At times we have found atendency for an insoluble mass to form or at least to obtain incipient cross-linking or gelling evenwhen the molal ratio is in the order of 2 moles of resin to one of diepoxide. We have found this can be avoided by any one of the following procedures or their equivalent. Dilute the resin or the diepoxide, or both, with an inert solvent, such as xylene or the like. In some instances an oxygenated solvent, such as the diethylether of ethyleneglycol may be ema ployed. Another procedure which is helpful is to reduce the amount of catalyst used, or reduce the temperature of reaction by adding a small amount of initially lower boiling solvent, such as benzene, or use benzene entirely. Also, we have found it desirable at times to use slightly less than apparently the theoretical amount of diepoxide', for instance, 90% to 95% instead of 100%. The reason for this fact may reside in the possibility that the molecular weight dimensions on either the resin mole or polyamine had been used, and may be indicated in the following manner:

[Oxyalkylated(Amine)CH (Resin) 1 When a diglycidyl ether is employed one would obviously obtain compounds in which two molecules of the Oxyalkylated(Amine)OHKResiul L l Oxyalkylated (Amine) CH2 Resin) Likewise, it is obvious that the two different types of aeewse oxyalkylation-susceptible compounds may combine so as to give molecules which may be indicated thus:

gimme) CHz(xya1kylatcd Resin) CHzLAmine} F I Oxyalkylated Amine) CH2 Resin) Oxyalkylated (Amine) CHz(Amine) l i t l 1 (Amine) OH2(Oxya1kylated Resin) CHM Amine) Oxyalkylated (Amine) C Hz(Amine) I l' 'l Oxyalkylated (Amine) CH2 (Resin) 0 xyalkylated (Amine) 0 H2 (Amine) l l Actually, the product obtained by reaction with a diglycidyl ether could show considerably greater complexity due to the fact that, as previously pointed out, the condensate reaction probably does not yield a hundred percent condensate in absence of other byproducts. All this simply emphasizes one fact, to wit, that there is no suitable method of characterizing the final reaction product except in terms of method of manufacture.

PART 7 As to the use of conventional demulsifying agents reference is made to U. S. Patent No. 2,626,929, dated January 7, 1953, to De Groote, and particularly to Part 3. Everything that appears therein applies with equal force and effect to the instant process, noting only that where reference is made to Example 13b in said text beginning in column 15 and ending in column 18, reference should be to Example 32, herein described.

PART 8 The products, compounds, or the like, herein described can be employed for various purposes and particularly for the resolution of petroleum emulsions of the waterin-oil type as described in detail in Part 7, preceding.

Such products can be reacted with alkylene imines, such as ethylene imine or propylene imine, to produce cation-active materials. Instead of an imine one may employ what is a somewhat equivalent material, to wit, a dialkylaminoepoxypropane of the structure their use in the resolution of petroleum emulsions they may be used as emulsifying agents for oils, fats, and waxes, as ingredients in insecticide compositions, or as detergents and wetting agents in the laundering, scouring, drying, tanning and mordanting industries. They may also be used for preparing boring or metal-cutting oils and cattle dips, as metal pickling inhibitors, and for pharmaceutical purposes.

Not only do these oxyalkylated derivatives have utility as such but they can serve as initial materials for more complicated reactions of the kind ordinarily requiring a hydroxyl radical. This includes esterification, etherization, etc.

The oxyalkylated derivatives may be used as valuable additives to lubricating oils, both those derived from petroleum and synthetic lubricating oils. Also, they can be used as additives to hydraulic brake fluids of the aqueous and non-aqueous types. They may be used in connection with other processes where they are injected into an oil or gas well for purpose of removing a mud sheath, increasing the ultimate flow of fluid from the surrounding strata, and particularly in secondary recovery operations using aqueous flood waters. These derivatives also are suitable for use in dry cleaners soaps.

More specifically, such products, depending on the nature of the initial resin, the particular monoepoxide selected and the ratio of monoepoxide to resin, together with the particular polyepoxide employed, resultin a variety of materials which are useful as wetting agents or surface tension reducing agents; as detergents, emulsifiers or dispersing agents; as additives for lubricants, both of the natural petroleum type and the synthetic type, as additives in the flotation of ores, and at times as aids in chemical reactions insofar that demulsification is produced between the insoluble reactants. Furthermore, such products can be used for a variety of other purposes, including use as corrosion inhibitors, defoamers, asphalt additives, and at times even in the resolution of oil-in-water emulsions. They serve at times as mutual solvents promoting a homogeneous system from two otherwise insoluble phases.

The products herein described can be reacted with polycarboxy acids, such as phthalic acid or anhydride, maleic acid or anhydride, diglycolic acid, and various tricarboxy and tetracarboxy acids so as to yield acylated derivatives, particularly if one employs one mole of the polycarboxy acid for each reactive hydroxyl radical present in the final polyepoxide-treated product. Thus, one obtains a comparatively large molecule in which there is a plurality of carboxyl radicals. Such acidic fractional esters are suitable for the resolution of petroleum emulsions of the water-in-oil type as herein described.

Having thus described our invention what we claim as new and desire to secure by Letters Patent is:

1. A three-step manufacturing process involving (1) condensation; (2) oxyalkylation with a monoepoxide; and (3) oxyalkylation with a polyepoxide; said first manufacturing step being a method of producing a resin condensate by (A) condensing (a) an oxyalkylation-susceptible, fusible, nonoxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula 31 in which R is a saturated aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufliciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat stable and oxyalkylation-susceptible; followed as a second step by (B) oxyalkylation by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide to produce a monoepoxide oxyalkylated resin condensate; and then completing the reaction by a third step of (C) reacting said monoepoxide oxyalkylated resin condensate with nonaryl hydrophile polyepoxides containing at least two 1,2-epoxy rings and having two ter-- minal 1,2-epoxy rings obtained by replacement of an oxygen-linked hydrogen atom in a water-soluble polyhydric alcohol by the radical H H H %-C\/CH said polyepoxides being free from reactive functional groups other than 1,2-epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane rings is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; with the further proviso that said reactive monoepoxideoxyalkylated resin condensate and nonaryl polyepoxides be members of the class consisting of nontherrnosetting organic solvent-soluble liquids and solids melting below the point of pyrolysis; with the added proviso that the reaction product be a member of the class of solvent-soluble liquid and solids melting below the point of pyrolysis; said reaction between the monoepoxide-oxyalkylated resin condensate and the nonaryl poyyepoxide being conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the oxyalkylated resin condensate to 1 mole of the nonaryl polyepoxide.

2. A three-step manufacturing process involving (1) condensation; (2) oxyalkylation with a monoepoxide; and 3) oxyalkylation with a polyepoxide; said first manufacturing step being a method of producing a resin condensate by (A) condensing (a) an oxyalkylation-susceptible, fusible, nonoxygenated organic solvent-soluble; water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a saturated aliphatic hydrocarbon radical having atleast 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate Water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed as a second step by (B) oxyalkylation by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide to produce a monoepoxide oxyalkylated resin condensate; and then completing the reaction by a third step of (C) reacting said monoepoxide oxyalkylated resin condensate with nonaryl hydrophile polyepoxides containing at least two 1,2-epoxy rings and having two terminal 1,2-epoxy rings obtained by replacement of an oxygen-linked hydrogen atom in a water-soluble polyhydric alcohol by the radical said polyepoxides being free from reactive functional groups other than 1,2-epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane rings is free from any radical having more than 4 uninterrupted carbon atoms in a, single chain; said polyepoxides being characterized by having present not more than 20 carbon atoms; with the further proviso that said reactive monoepoxideoxyalkylated resin condensate and nonaryl polyepoxides be members of the class consisting of non-thermosetting organic solventsoluble liquids and solids melting below the point of pyrolysis; with the added proviso that the reaction product be a member of the class of solvent-soluble liquids and solids melting below the point'of pyrolysis; said reaction between the monoepoxide-oxyalkylated resin conclensate and the nonaryl polyepoxide being conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the oxyalkylated resin condensate to 1 mole of the nonaryl polyepoxide.

3. A three-step manufacturing process involving 1) condensation; (2) oxyalkylation with a monoepoxide; and (3) oxyalkylation with a diepoxide; said first manufacturing step being a method of producing a resin condensate by (A) condensing (a) an oxyalkylation-susceptible, fusible, nonoxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a saturated aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (0) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed as a second step by (B) oxyalkylation by means of an alphabeta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide to produce a monoepoxide oxyalkylated resin con- 33 densate; and then completing the reaction by a third step of (C) reacting said monoepoxide oxyalkylated resin condensate with nonaryl hydrophile diepoxides containing two terminal 1,2-epoxy rings obtained by replacement of an oxygen-linked hydrogen atom in a water-soluble polyhydric alcohol by the radical said diepoxide being free from reactive functional groups other than 1,2-epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane rings is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; said diepoxides being characterized by having present not more than 20 carbon atoms; with the further proviso that said reactive monoepoxideoxyalkylated resin condensate and nonaryl diepoxides be members of the class consisting of non-thermosetting organic solvent-soluble liquids and solids melting below the point of pyrolysis; with the added proviso that the reaction product be a member of the class of solvent-soluble liquids and solids melting below the point of pyrolysis; said reaction between the Inonoepoxide-oxyalkylated resin condensate and the nonaryl diepoxide being conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the oxyalkylated resin condensate to 1 mole of the nonaryl diepoxide.

4. The process of claim 3 wherein the diepoxide contains at least one reactive hydroxyl radical.

5. A three-step manufacturing process involving 1) condensation; (2) oxyalkylation with a monoepoxide; and (3) oxyalkylation with a diepoxide; said first manufacturing step being a method of producing a resin condensate by (A) condensing (a) an oxyalkylation-susceptible, fusible, nonoxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a :difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a saturated aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and formaldehyde; said condensation reaction being conducted at a temperature sufliciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed as a second step by (B) oxyalkylation by means of an alphabeta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide to produce a monoepoxide oxyalkylated resin condensate; and then completing the reaction by a third step of (C) reacting said monoepoxide oxyalkylated resin condensate with a hydroxylated diepoxypolyglycerol containing two terminal 1,2-epoxy rings and having not more than 20 carbon atoms; with the further proviso that said monoepoxide-oxyalkylated resin condensate and said hydroxylated diepoxyglycerol be members of the class consisting of non-thermosetting organic solvent-soluble liquids and solids melting below the point of pyrolysis; with the added proviso that the reaction product be a member of the class of solvent-soluble liquids and solids melting below the point of pyrolysis; said reaction between the monoepoxide-oxyalkylated resin condensate and the hydroxylated diepoxypolyglycerol being conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the oxyalkylated resin condensate to 1 mole of the hydroxylated diepoxyglycerol.

6. The method of claim 5 wherein the hydroxylated diepoxypolyglycerol has not over 5 glycerol nuclei.

7. The method of claim 5 wherein the hydroxylated diepoxypolyglycerol has not over 5 glycerol nuclei and the difunctional monohydric phenol employed in forming the initial phenol-aldehyde resin is para-substituted.

8. The method of claim 5 wherein the hydroxylated diepoxypolyglycerol has not over 5 glycerol nuclei, and the difunctional monohydric phenol employed in forming the initial phenol-aldehyde resin is para-substituted and contains at least 4 and not over 14 carbon atoms in the substituent group.

9. The method of claim 5 wherein the hydroxylated diepoxypolyglycerol has not over 5 glycerol nuclei, and the difunctional monohydric phenol employed in forming the initial phenol-aldehyde resin is para-substituted and contains at least 4 and not over 14 carbon atoms in the substituent group, and the aldehyde employed in forming the initial phenol-aldehyde resin is formaldehyde.

10. The method of claim 5 wherein the hydroxylated diepoxypolyglycerol has not over 5 glycerol nuclei, and the difunctional monohydric phenol employed in forming the initial phenol-aldehyde resin is para-substituted and contains at least 4 and not over 14 carbon atoms in the substituent group, and the aldehyde employed in forming the initial phenol-aldehyde resin is formaldehyde, and the total number of phenolic nuclei in the initial resin are not over 5.

11. The product obtained by the method described in claim 1.

12. The product obtained by the method described in claim 10.

No references cited. 

1. A THREE-STEP MANUFACTURING PROCESS INVOLVING (1) CONDENSATION; (2) OXYALKYLATION WITH A MONOEPOXIDE; AND (3) OXYALKYLATION WITH A POLYEPOXIDE; SAID FIRST MANUFACTURING STEP BEING A METHOD OF PRODUCING A RESIN CONDENSATE BY (A) CONDENSING (A) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, NONOXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIOINAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 